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WO2022040486A1 - Amélioration de la sensibilisation d'une conversion ascendante de photons à l'état solide - Google Patents

Amélioration de la sensibilisation d'une conversion ascendante de photons à l'état solide Download PDF

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Publication number
WO2022040486A1
WO2022040486A1 PCT/US2021/046801 US2021046801W WO2022040486A1 WO 2022040486 A1 WO2022040486 A1 WO 2022040486A1 US 2021046801 W US2021046801 W US 2021046801W WO 2022040486 A1 WO2022040486 A1 WO 2022040486A1
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Prior art keywords
sensitizer
conjugated polymer
less
composition
cep
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Inventor
Sean Shaheen
Daniel WEINGARTEN
Michael LACOUNT
Mark T. LUSK
Jao Van De Lagemaat
Garry RUMBLES
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Alliance for Sustainable Energy LLC
Colorado School of Mines
University of Colorado System
University of Colorado Colorado Springs
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Alliance for Sustainable Energy LLC
Colorado School of Mines
University of Colorado System
University of Colorado Colorado Springs
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Priority to US18/022,203 priority Critical patent/US20230313032A1/en
Publication of WO2022040486A1 publication Critical patent/WO2022040486A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N5/00—Radiation therapy
    • A61N5/06—Radiation therapy using light
    • A61N5/0613—Apparatus adapted for a specific treatment
    • A61N5/062—Photodynamic therapy, i.e. excitation of an agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • C09B67/0063—Preparation of organic pigments of organic pigments with only macromolecular substances
    • C09B67/0064—Preparation of organic pigments of organic pigments with only macromolecular substances of phthalocynanines with only macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/124—Copolymers alternating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/312—Non-condensed aromatic systems, e.g. benzene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
    • C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/52—Luminescence
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1416—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1425—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1433—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B

Definitions

  • Upconversion materials have potential applications in a wide-range of fields, such as biosensing, chemical sensing, in vivo imaging, drug delivery, photodynamic therapy and photoactivation.
  • Upconverting luminescence refers to an anti-Stokes type process in which the sequential absorption of two or more photons leads to the emission of light at shorter wavelength (e.g., ultraviolet, visible, and near-infrared) than the excitation wavelength.
  • shorter wavelength e.g., ultraviolet, visible, and near-infrared
  • Cooperative energy pooling is an energy transfer mechanism that provides an alternative route towards efficient and applicable photon upconversion.
  • CEP is the process of two photoexcited sensitizer chromophores non-radiatively transferring their energy to a single higher-energy state in an acceptor chromophore.
  • Theoretical work modelling three-body FRET processes in the late 1990s laid the foundation for a quantum electrodynamical understanding of the CEP process and more recent computational work has highlighted the dependence of the CEP process on both the separation distance and relative orientations of sensitizer and acceptor chromophores. There is a clear need for the development of systems having improved CEP yields over the previous systems.
  • compositions, systems, and methods based on polymer-based cooperative energy pooling (CEP) systems.
  • CEP polymer-based cooperative energy pooling
  • Two distinct polymer-based CEP systems are exemplified herein, both of which presented improved CEP yields over Rhod6G/Stilb420 CEP system.
  • Measurements of the internal quantum yield of CEP within the CEP systems are also provided.
  • Femtosecond-scale transient absorption spectroscopy (TAS) data are also provided, displaying the CEP energy transfer process with time-resolution to clearly observe the energy transfer from sensitizers to acceptor.
  • methods for enhancing upconversion luminescence of a solid phase composition comprising a multi-photon absorbing conjugated polymer and a sensitizer, wherein the conjugated polymer is separated from the sensitizer by an average distance of 5 nm or less are provided.
  • the method can include irradiating the composition at a wavelength corresponding to the sensitizer absorption thereby generating a plurality of photoexcited sensitizers, allowing the plurality of photoexcited sensitizers to simultaneously transfer their energies to a higher- energy state on the conjugated polymer, wherein the emission spectrum of the photoexcited sensitizer at least partially overlaps with the multi-photon absorption spectrum of the conjugated polymer, such that there is resonant coupling between the sensitizer transition dipole and the conjugated polymer multi-photon tensor, and detecting luminescence in a spectral region characteristic of the conjugated polymer activated by the photoexcited sensitizers.
  • the emission spectrum of the conjugated polymer exhibits negligible overlap with the absorption spectrum of the sensitizer.
  • the multi-photon absorbing conjugated polymer can be a two-photon absorbing conjugated polymer.
  • the conjugated polymer can comprise a polyfluorene, a polyarylene, a polyphenylene, a polyanthracene, a polypyrene, a phenanthrene, a heterocyclic polyarylene such as a poly(thienylene), a poly(pyridine), an oxadiazole-containing polymer, a quinoline-containing polymer, a silole-containing polymer, a poly(3 -alkylthiophene), or a combination thereof.
  • the conjugated polymer comprises a polyfluorene, such as a polyfluorene selected from the group consisting of:
  • the sensitizer can, for example, comprise a near infrared absorbing organic chromophore.
  • the sensitizer can comprise a cationic dye, an anionic dye, a nonionic dye, an amphoteric dye, a metal-ligand complex, fluorescein, chlorophyll, a phthalocyanine, an indodicarbocyanine, or a mixture thereof.
  • the sensitizer comprises zinc phthalocyanine (ZnPC) (structure shown below), 1,1, 3,3,3, 3-Hexamethyl- indodicarbocyanine iodide (HIDC) (structure shown below), or a combination thereof which structures are shown below.
  • the amount of sensitizer and conjugated polymer in the composition can vary.
  • the molar ratio of the sensitizer to the conjugated polymer can be from 1 : 10 to 1 : 100 (e.g., from 1 :20 to 1 :60, or from 1 :30 to 1 :50). In some examples, the molar ratio of the sensitizer to the conjugated polymer can be 1 :40.
  • the composition comprising the conjugated polymer and sensitizer is a solid phase composition.
  • the solid phase composition can be in the form of a nanofilm or a nanoparticle, e.g. to facilitate optimum sensitizer-acceptor separation distance for increasing the overall rate and yield of CEP upconversion.
  • the composition is a nanofilm having an average thickness of 500 nm or less (e.g., 350 nm or less, or 300 nm or less). In some examples, the nanofilm has an average thickness of from 50 to 500 nm, from 100 to 300 nm, or from 200 to 300 nm.
  • the composition comprises nanoparticles having an average particle size of 500 nm or less (e.g., 350 nm or less, or 300 nm or less). In some examples, the nanoparticles have an average particle size of from 50 to 500 nm, from 100 to 300 nm, or from 200 to 300 nm.
  • systems for enhancing upconversion luminescence are also disclosed.
  • the systems can further include a source of radiation for irradiating the solid-phase composition at a wavelength corresponding to the sensitizer absorption.
  • systems for enhancing upconversion luminescence comprising: a solid phase composition comprising a multi-photon absorbing conjugated polymer and a sensitizer, wherein the solid phase composition is in the form of a nanofilm or nanoparticles, and wherein the conjugated polymer is separated from the sensitizer by an average distance of 5 nm or less; wherein the emission spectrum of the sensitizer at least partially overlaps with the multi-photon absorption spectrum of the conjugated polymer, such that when the sensitizer becomes electronically excited, there is resonant coupling between the sensitizer transition dipole and the conjugated polymer multi-photon tensor; and a source of radiation for irradiating the composition at a wavelength corresponding to the sensitizer absorption.
  • the sensitizer and the multi-photon absorbing conjugated polymer are in a molar ratio from 1 : 10 to 1 : 100, from 1 :20 to 1 :60, or from 1 :30 to 1 :50. In some examples of the systems, the sensitizer and the multi -photon absorbing conjugated polymer are in a molar ratio of 1 :40.
  • the multi-photon absorbing conjugated polymer is a two-photon absorbing conjugated polymer.
  • the emission spectrum of the conjugated polymer exhibits negligible overlap with the absorption spectrum of the sensitizer.
  • the conjugated polymer comprises a polyfluorene, a polyarylene, a polyphenylene, a polyanthracene, a polypyrene, a phenanthrene, a heterocyclic polyarylene such as a poly(thienylene), a poly(pyridine), an oxadiazole-containing polymer, a quinoline-containing polymer, a silole-containing polymer, a poly(3-alkyl-thiophene), or a combination thereof.
  • the conjugated polymer comprises a polyfluorene.
  • the conjugated polymer comprises a polyfluorene selected from the group consisting of: combinations thereof.
  • the sensitizer comprises a near infrared absorbing organic chromophore.
  • the sensitizer is selected from a cationic dye, an anionic dye, a nonionic dye, an amphoteric dye, a metal-ligand complex, fluorescein, chlorophyll, a phthalocyanine, an indodicarbocyanine, or a mixture thereof.
  • the sensitizer comprises: or a combination thereof.
  • the composition is a nanofilm having an average thickness of 500 nm or less, 350 nm or less, or 300 nm or less. In some examples of the systems, the nanofilm has an average thickness of from 50 nm to 500 nm, from 100 nm to 300 nm, or 200 to 300 nm.
  • the composition comprises nanoparticles having an average particle size of 500 nm or less, 350 nm or less, or 300 nm or less. In some examples of the systems, the nanoparticles have an average particle size of from 50 nm to 500 nm, from 100 nm to 300 nm, or from 200 to 300 nm.
  • compositions for enhancing upconversion luminescence comprising: a solid phase composition comprising multi-photon absorbing conjugated polymer and a sensitizer, wherein the solid phase composition is in the form of a nanofilm or nanoparticles, and wherein the conjugated polymer is separated from the sensitizer by an average distance of 5 nm or less; wherein the emission spectrum of the sensitizer at least partially overlaps with the multi-photon absorption spectrum of the conjugated polymer, such that when the sensitizer becomes electronically excited, there is resonant coupling between the sensitizer transition dipole and the conjugated polymer multi-photon tensor; and wherein the sensitizer and the multi -photon absorbing conjugated polymer are in a molar ratio from 1 : 10 to 1 : 100, from 1 :20 to 1 :60, or from 1 :30 to 1 :50.
  • the sensitizer and the multi-photon absorbing conjugated polymer are in a molar ratio from 1 : 10 to 1
  • the multi-photon absorbing conjugated polymer is a two-photon absorbing conjugated polymer.
  • the emission spectrum of the conjugated polymer exhibits negligible overlap with the absorption spectrum of the sensitizer.
  • the conjugated polymer comprises a polyfluorene, a polyarylene, a polyphenylene, a polyanthracene, a polypyrene, a phenanthrene, a heterocyclic polyarylene such as a poly(thienylene), a poly(pyridine), an oxadiazole-containing polymer, a quinoline-containing polymer, a silole-containing polymer, a poly(3-alkyl-thiophene), or a combination thereof.
  • the conjugated polymer comprises a polyfluorene.
  • the conjugated polymer comprises a polyfluorene selected from the group consisting of:
  • the sensitizer comprises a near infrared absorbing organic chromophore.
  • the sensitizer is selected from a cationic dye, an anionic dye, a nonionic dye, an amphoteric dye, a metal-ligand complex, fluorescein, chlorophyll, a phthalocyanine, an indodicarbocyanine, or a mixture thereof.
  • the sensitizer comprises: or a combination thereof.
  • the composition is a nanofilm having an average thickness of 500 nm or less, 350 nm or less, or 300 nm or less. In some examples of the compositions, the nanofilm has an average thickness of from 50 nm to 500 nm, from 100 nm to 300 nm, or from 200 to 300 nm.
  • the composition comprises nanoparticles having an average particle size of 500 nm or less, 350 nm or less, or 300 nm or less. In some examples of the compositions, the nanoparticles have an average particle size of from 50 nm to 500 nm, from 100 nm to 300 nm, or from 200 to 300 nm.
  • the composition, methods, and systems described herein has applications in fields including biomedical imaging, biomedical therapeutics and cancer treatments, optical communications, optical computing, and solar energy conversion.
  • imaging methods comprising, administering to a subject a composition as described herein, irradiating the composition at a wavelength corresponding to the sensitizer absorption, and detecting luminescence in a spectral region characteristic of the conjugated polymer activated by the plurality of photoexcited sensitizers are provided.
  • Optoelectronic signaling devices comprising a composition as described herein, preferably wherein the device is for optical communication, optical computing, or solar energy conversion are also provided.
  • FIG. 1A shows the molecular structure of ADS259BE.
  • FIG. IB shows the molecular structure of ADS128GE.
  • FIG. 1C shows the molecular structure of ADS329BE.
  • FIG. ID shows the molecular structure of ADS251BE.
  • FIG. IE shows the molecular structure of zinc phthalocyanine.
  • FIG. IF shows the molecular structure of HIDC iodide.
  • FIG. 2A is a graph showing the spectral properties of ZnPC/ADS128 CEP system. Normalized absorption, emission, and upconverted emission spectra of ZnPC/ADS128 blend film. Upconverted emission was measured under excitation at 677 nm. The emission spectrum is cut off due to the use of a 500 nm shortpass filter to prevent scattered excitation light from contaminating the upconverted signal. Normal emission was measured using 330 nm excitation light.
  • FIG. 2B is a graph showing the spectral properties of ZnPC/ADS128 CEP system. Normalized absorption and emission spectra of ADS 128 (acceptor) and ZnPC (sensitizer) in pristine solutions with THF solvent. Steady-state emission spectra were measured under excitation at 350 nm.
  • FIG. 3A is a graph showing the spectral properties of HIDC/ADS259 CEP system. Normalized absorption, emission, and upconverted emission spectra of HIDC/ADS259 blend film. Upconverted emission was measured under excitation at 664 nm. The emission spectrum is cut off due to the use of a 500 nm shortpass filter to prevent scattered excitation light from contaminating the upconverted signal. Normal emission was measured using 390 nm excitation light. Magnified red emission peak measured under excitation at 590 nm to target sensitizer absorption.
  • FIG. 3B is a graph showing the spectral properties of HIDC/ADS259 CEP system. Normalized absorption and emission spectra of ADS259 (acceptor) and HIDC (sensitizer) in pristine solutions with THF solvent. Steady-state emission spectra were measured under excitation at 330 nm and 520 nm for ADS259 and HIDC, respectively.
  • FIG. 4A is a graph showing the excitation dependence of ZnPC/ADS128 blend films.
  • the squares indicate the measured upconverted emission at 486 nm from ZnPC/ADS128 blend films as a function of 677 nm excitation intensity plotted on a log-log scale.
  • the indicated lines are quadratic and linear fits to the first and last three data points, respectively.
  • the black circles represent the instantaneous power-law dependence of the measured excitation dependence as determined by the slope of a linear fit to a sliding boxcar window of eight points on the log-log plot of the excitation dependence data.
  • FIG. 4B is a graph showing the excitation dependence of HIDC/ADS259 blend films.
  • the squares indicate the measured upconverted emission at 436 nm from HIDC/ADS259 blend films as a function of 664 nm excitation intensity plotted on a log-log scale.
  • the indicated lines are quadratic and linear fits to the first and last three data points, respectively.
  • the black circles represent the instantaneous power-law dependence of the measured excitation dependence as determined by the slope of a linear fit to a sliding boxcar window of eight points on the log-log plot of the excitation dependence data.
  • FIG. 5A is a graphs showing TA spectra of pristine ADS 128 thin films. When excited at 400 nm the ADS 128 polymer displays two noticeable features at 469 nm and 515 nm with a slight should feature at 555 nm, all with - A OD peaks. The 515 nm peak and the shoulder feature are nearly absent after 150 ps, indicating that the different features each have distinct lifetimes.
  • FIG. 5B is a graph showing TA spectra of pristine ZnPC thin films.
  • the ZnPC sensitizer When excited at 677 nm the ZnPC sensitizer displays a main + A OD plateau feature stretching between -430-600 nm, with slight sub-features at 485 nm, 530 nm, and 596 nm. Since the shape of the spectrum changes over time the different features must have slightly different lifetimes, but the data was too noisy for accurate fitting of the distinct decay lifetimes. The overall lifetime of the ZnPC excited state is noticeably longer than the ADS128 excited state lifetimes.
  • FIG. 6A is a graph showing the TA spectra of ADS128/ZnPC CEP film.
  • FIG. 6B is a graph showing the TA spectra of ADS128/ZnPC CEP film.
  • Kinetic traces corresponding at the wavelengths of the component chromophore features are displayed on a normalized AOD axis to facilitate comparison of rise-times and decay times.
  • the previously distinct features above 485 nm all appear with similar decay times.
  • the kinetics at 469 nm show a delayed rise to +AOD corresponding to the ZnPC excited stat, and subsequent a decay to -AOD corresponding to a delayed rise of the ADS 128 excited state and indicating CEP.
  • an anionic dye includes a plurality of anionic dyes, including mixtures thereof.
  • the terms “may,” “optionally,” and “may optionally” are used interchangeably and are meant to include cases in which the condition occurs as well as cases in which the condition does not occur.
  • the statement that a formulation “may include an excipient” is meant to include cases in which the formulation includes an excipient as well as cases in which the formulation does not include an excipient.
  • Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as "about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed.
  • Average generally refers to the statistical mean value.
  • substantially is meant within 5%, e.g., within 4%, 3%, 2%, or 1%.
  • A, B, C, or combinations thereof refers to all permutations and combinations of the listed items preceding the term.
  • “A, B, C, or combinations thereof’ is intended to include at least one of A, B, C, AB, AC, BC, or ABC, and if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB.
  • expressly included are combinations that contain repeats of one or more item or term, such as BB, AAA, AB, BBC, AAABCCCC, CBBAAA, CAB ABB, and so forth.
  • the skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from the context.
  • a “subject” is meant an individual.
  • the “subject” can include domesticated animals (e.g., cats, dogs, etc.), livestock (e.g., cattle, horses, pigs, sheep, goats, etc.), laboratory animals (e.g., mouse, rabbit, rat, guinea pig, etc.), and birds.
  • “Subject” can also include a mammal, such as a primate or a human.
  • the subject can be a human or veterinary patient.
  • patient refers to a subject under the treatment of a clinician, e.g., physician.
  • molecular weight refers to number average molecular weight as measured by 'H N R spectroscopy, unless indicated otherwise.
  • Polymer means a material formed by polymerizing one or more monomers.
  • (co)polymer includes homopolymers, copolymers, or mixtures thereof.
  • (meth)acryl includes “acryl ... ,” “methacryl ... ,” or mixtures thereof.
  • biocompatible describes a material that elicits an appropriate host response without any adverse effects, and is compatible with living cells, tissues, organs, or systems, and posing no risk of injury, toxicity, or rejection by the immune system.
  • upconversion refers to a process in which the sequential absorption of two or more photons leads to the emission of light at shorter wavelength than the excitation wavelength.
  • sensitizer refers to a molecule that absorbs energy (such as infrared energy) and transfers this energy non-radiatively to the activator.
  • activator refers to a molecule which receives energy from the sensitizer and as a consequence thereof emits upconversion luminescence.
  • CEP singlet-based cooperative energy pooling
  • CEP is more likely to occur when there is a minimal separation distance between the sensitizers and the acceptor, and hence CEP energy transfer is likely to preferentially occur to acceptor chromophores whose nearest neighbors are sensitizers rather than other acceptors.
  • This isolation from other acceptors then potentially extends the lifetime of the CEP-excited state towards its inherent radiative lifetime by reducing pathways for non-radiative decay via selfquenching.
  • heterogeneity of the CEP composition morphology plays important role in the CEP rates and excited state lifetimes.
  • compositions and systems based on polymer-based cooperative energy pooling (CEP) systems are provided herein.
  • the polymer-based CEP systems provided herein exhibit improved CEP over the previous generation CEP system as these systems have larger acceptor multi-photon absorption cross-sections that extends to longer wavelengths, which provide improved spectral overlap between acceptor and sensitizer, and reduced FRET energy loss pathways, all of which are factors that are expected to improve CEP rates.
  • compositions and systems herein comprise a polymer and a sensitizer.
  • the polymers used in the present compositions and systems are multi-photon absorption conjugated polymers.
  • the multi-photon absorption spectrum of the conjugated polymer at least partially overlaps with the emission spectrum of the sensitizer, such that when the sensitizer becomes electronically excited, there is resonant coupling between the sensitizer transition dipole and the conjugated polymer multi-photon tensor.
  • the multi-photon absorption spectrum refers to an absorption spectrum of an excited electronic state of a molecule (the conjugated polymer in this case) after the absorption of at least two photons of identical or different frequencies in order to excite the molecule from one state (usually the ground state) to a higher energy.
  • the multi-photon absorption spectrum of the conjugated polymer at least partially overlaps with the emission spectrum of the sensitizer.
  • the multi-photon absorption spectrum of the conjugated polymer can overlap with the emission spectrum of the sensitizer by 10% or more (e.g., 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, or 95% or more).
  • the multi-photon absorption spectrum of the conjugated polymer can overlap with the emission spectrum of the sensitizer by 100% or less (e.g., 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, or 15% or less).
  • the amount of overlap between the multi-photon absorption spectrum of the conjugated polymer and the emission spectrum of the sensitizer can range from any of the minimum values described above to any of the maximum values described above.
  • the multi-photon absorption spectrum of the conjugated polymer can overlap with the emission spectrum of the sensitizer by 10%-100% (e.g., from 10% to 45%, from 45% to 100%, from 10% to 40%, from 40% to 70%, from 70% to 100%, from 15% to 100%, from 10% to 95%, from 15% to 95%, or from 10% to 75%).
  • the emission spectrum of the conjugated polymer exhibits negligible to virtually no observable overlap with the absorption spectrum of the sensitizer.
  • the emission spectrum of the conjugated polymer overlaps with the absorption spectrum of the sensitizer by 10% or less (e.g., 9% or less, 8% or less, 7% or less, 6%, 5%, 4% or less, 3% or less, 2% or less, or 1% or less).
  • the multi-photon absorbing conjugated polymer can be a two-photon absorbing conjugated polymer.
  • the conjugated polymer can comprise a polyfluorene, a polyarylene, a polyphenylene, a polyanthracene, a polypyrene, a phenanthrene, a heterocyclic polyarylene such as a poly(thienylene), a poly(pyridine), an oxadiazole-containing polymer, a quinoline-containing polymer, a silole-containing polymer, a poly(3 -alkylthiophene), or a combination thereof.
  • conjugated polymers include, but are not limited to, a pyrrolyl, furanyl, imidazolyl, triazolyl, isoxazolyl, oxadiazolyl, furazanyl, pyridazinyl, pyrimidyl, pyrazinyl, triazinyl, tetrazinyl, benzofuranyl, benzothiophenyl, indolyl, isoindazolyl, benzimidazolyl, benzotri azolyl, benzoxazolyl, isoquinolyl, cinnolyl, quinazolyl, naphthyridyl, phthal azyl, phentri azyl, benzotetrazyl, carb azolyl, dibenzofuranyl, dibenzothiophenyl, acridyl, phenazyl, and combinations thereof.
  • the conjugated polymer comprises a polyfluorene, such as a polyfluorene selected from the group consisting of: combinations thereof.
  • the multi-photon absorption spectrum of the conjugated polymer at least partially overlaps with the emission spectrum of the sensitizer.
  • the multi-photon absorption spectrum of the conjugated polymer can overlap significantly with the emission spectrum of the sensitizer. This allows efficient coupling between the sensitizer transition dipole and the conjugated polymer’s multi -photon absorption tensor and hence a large CEP rate. Further, the use of sensitizers with high quantum yield even when aggregated can directly increase both the CEP rate but also the CEP radius.
  • the sensitizer can, for example, comprise a near infrared absorbing organic chromophore.
  • the sensitizer can comprise a cationic dye, an anionic dye, a nonionic dye, an amphoteric dye, a metal-ligand complex, fluorescein, chlorophyll, a phthalocyanine, an indodicarbocyanine, or a mixture thereof.
  • suitable sensitizers include zinc phthalocyanine (ZnPC) and 1,1, 3,3,3, 3-Hexamethyl- indodicarbocyanine iodide (HIDC), the structures of which are shown below.
  • the sensitizer can include ZnPC, HIDC, or a combination thereof.
  • the sensitizer When sensitized by the sensitizer, photons are primarily transferred to either acceptors (i.e., the conjugated polymer) or neighboring sensitizers. Consequently, photons will either be transferred to an activator leading to upconversion and resultant luminescence emission, or alternatively encounter a quencher. Where the sensitizer concentration exceeds a certain amount, the chance of sensitized photons encountering quenchers is also increased thereby contributing to concentration quenching.
  • the sensitizer is a low self-quenching chromophore which leads to improved CEP radius, increased overall absorbance of the blend film, and increased exciton diffusivity, all of which improve overall CEP yields.
  • One aspect of the CEP systems described herein is providing a blend of sensitizer and polymer such that the average sensitizer chromophores are isolated from other sensitizers.
  • the amount of sensitizer and conjugated polymer can be present in a molar ratio of the sensitizer to the conjugated polymer of 1 : 10 or more (e.g., 1 :20 or more, 1 :30 or more, 1 :40 or more, 1 :50 or more, 1 :60 or more, 1 :70 or more, 1 :80 or more, or 1 :90 or more).
  • the amount of sensitizer and conjugated polymer can be present in a molar ratio of the sensitizer to the conjugated polymer of 1 : 100 or less (e.g., 1 :90 or less, 1 :80 or less, 1 :70 or less, 1 :60 or less, 1 :50 or less, 1 :40 or less, 1 :30 or less, or 1 :20 or less).
  • the molar ratio of the sensitizer to the conjugated polymer can range from any of the minimum values described above to any of the maximum values described above.
  • the amount of sensitizer and conjugated polymer can be present in a molar ratio of the sensitizer to the conjugated polymer of from 1 : 10 to 1 : 100 (e.g., from 1 : 10 to 1 :45, from 1 :45 to 1 : 100, from 1 : 10 to 1 :40, from 1 :40 to 1 :70, from 1 :70 to 1 : 100, from 1 : 15 to 1 : 100, from 1 : 10 to 1 :95, from 1 : 15 to 1 :95, from 1 : 10 to 1 :80, from 1 : 10 to 1 :70, from 1 :20 to 1 :60, or from 1 :30 to 1 :50).
  • the amount of sensitizer and conjugated polymer can be present in a molar ratio of the sensitizer to the conjugated polymer of 1 : 40.
  • the composition comprising the conjugated polymer and sensitizer is a solid phase composition.
  • a solid phase composition provides several advantages as the solid matrix prevents or minimizes collisional quenching of the sensitizer and reduces solvent effects.
  • the solid phase also provides a relatively rigid environment conducive to long emission lifetime and high luminescence efficiency.
  • the solid phase composition can be in the form of a nanofilm or a nanoparticle to facilitate optimum sensitizer-acceptor separation distance for increasing the overall rate and yield of CEP upconversion.
  • the shape of the nanoparticles can vary.
  • the nanoparticles can include spherical particles, non-spherical particles (such as elongated particles, cylindrical particles, rod-like particles, or any irregularly shaped particles), or combinations thereof.
  • the approximate sensitizer-acceptor chromophore separation distance can be calculated. Adjustments to the nanofilm or nanoparticle morphology can reduce the separation distance of the sensitizer-acceptor chromophore and increase the overall rate and yield of CEP upconversion.
  • the sensitizer is separated from the acceptor (conjugated polymer) by an average distance of no more than 5 nm (e.g., 5 nm or less, 4.5 nm or less, 4 nm or less, 3.5 nm or less, 3 nm or less, or 2.5 nm or less).
  • the nanofilms can have an average thickness of 1 micrometer (pm, micron) or less (e.g., 750 nanometers (nm) or less, 500 nm or less, 400 nm or less, 300 nm or less, 250 nm or less, 200 nm or less, 175 nm or less, 150 nm or less, 125 nm or less, 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, 60 nm or less, 50 nm or less, 45 nm or less, 40 nm or less, 35 nm or less, 30 nm or less, 25 nm or less, 15 nm or less, 10 nm or less, or 5 nm or less).
  • nm micrometer
  • the nanofilms can have an average thickness of 1 nanometer (nm) or more (e.g., 2 nm or more, 3 nm or more, 4 nm or more, 5 nm or more, 10 nm or more, 15 nm or more, or 25 nm or more, 30 nm or more, 35 nm or more, 40 nm or more, 45 nm or more, 50 nm or more, 60 nm or more, 70 nm or more, 80 nm or more, 90 nm or more, 100 nm or more, 125 nm or more, 150 nm or more, 175 nm or more, 200 nm or more, 250 nm or more, 300 nm or more, 400 nm or more, 500 nm or more, or 750 nm or more).
  • nm nanometer
  • the nanofilms can have an average thickness ranging from any of the minimum values described above to any of the maximum values described above.
  • the nanofilms can have an average thickness of from 1 nm to 1000 nm (e.g., from 1 nm to 500 nm, from 500 nm to 1000 nm, from 1 nm to 200 nm, from 200 nm to 400 nm, from 400 nm to 600 nm, from 600 nm to 800 nm, from 800 nm to 1000 nm, from 5 nm to 1000 nm, from 1 nm to 900 nm, from 5 nm to 900 nm, from 1 nm to 750 nm, from 5 nm to 500 nm, from 50 to 500 nm, from 100 nm to 500 nm, from 100 nm to 350 nm, from 150 nm to 300 nm, from 100 to 300 nm, from 50 nm to 300 nm.
  • the nanoparticles can have an average particle size.
  • Average particle size and “mean particle size” are used interchangeably herein, and generally refer to the statistical mean particle size of the particles in a population of particles.
  • the average particle size for a plurality of particles with a substantially spherical shape can comprise the average diameter of the plurality of particles.
  • the diameter of a particle can refer, for example, to the hydrodynamic diameter.
  • the hydrodynamic diameter of a particle can refer to the largest linear distance between two points on the surface of the particle.
  • Mean particle size can be measured using methods known in the art, such as evaluation by microscopy (e.g. electron microscopy) and/or dynamic light scattering.
  • the nanoparticles can have an average particle size of 1 micron or less (e.g., 750 nm or less, 500 nm or less, 400 nm or less, 300 nm or less, 250 nm or less, 200 nm or less, 175 nm or less, 150 nm or less, 125 nm or less, 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, 60 nm or less, 50 nm or less, 45 nm or less, 40 nm or less, 35 nm or less, 30 nm or less, 25 nm or less, 20 nm or less, 15 nm or less, 10 nm or less, or 5 nm or less).
  • 1 micron or less e.g., 750 nm or less, 500 nm or less, 400 nm or less, 300 nm or less, 250 nm or less, 200 nm or less, 175
  • the nanoparticles can have an average particle size of 1 nm or more (e.g., 2 nm or more, 3 nm or more, 4 or more, 5 nm or more, 10 nm or more, 15 nm or more, 25 nm or more, 30 nm or more, 35 nm or more, 40 nm or more, 45 nm or more, 50 nm or more, 60 nm or more, 70 nm or more, 80 nm or more, 90 nm or more, 100 nm or more, 125 nm or more, 150 nm or more, 175 nm or more, 200 nm or more, 250 nm or more, 300 nm or more, 400 nm or more, 500 nm or more, or 750 nm or more).
  • 1 nm or more e.g., 2 nm or more, 3 nm or more, 4 or more, 5 nm or more, 10 nm or more, 15
  • the nanoparticles can have an average particle size ranging from any of the minimum values described above to any of the maximum values described above.
  • the nanoparticles can have an average particle size of from 1 nm to 1000 nm (e.g., from 1 nm to 500 nm, from 500 nm to 1000 nm, from 1 nm to 200 nm, from 200 nm to 400 nm, from 400 nm to 600 nm, from 600 nm to 800 nm, from 800 nm to 1000 nm, from 5 nm to 1000 nm, from 1 nm to 900 nm, from 5 nm to 900 nm, from 1 nm to 750 nm, from 5 nm to 500 nm, from 50 nm to 500 nm, from 100 nm to 500 nm, from 100 nm to 350 nm, from 100 nm to 300 nm, from 150 nm to 300 nm,
  • the systems can further include a source of radiation for irradiating the solid-phase composition at a wavelength corresponding to the sensitizer absorption.
  • the source of radiation will depend on the particular sensitizer-acceptor chromophores used.
  • the sensitizer-acceptor chromophores can be a NIR-to-visible upconversion fluorescent composition.
  • the source of excitation can be NIR.
  • the means for delivery of the source of radiation to the system can be, for example, via optical fibers, endoscopes, external light, and external laser.
  • the articles can include optoelectronic devices including a display device, a solar cell, an optical data storage, a bio-probe, a carrier for drug delivery, a lamp, a LED, a LCD, a wear resistance, a laser, optical amplifier, a device for bio-imaging, optical communication, or optical computing.
  • optoelectronic devices including a display device, a solar cell, an optical data storage, a bio-probe, a carrier for drug delivery, a lamp, a LED, a LCD, a wear resistance, a laser, optical amplifier, a device for bio-imaging, optical communication, or optical computing.
  • optoelectronic signaling devices comprising a composition (e.g., the solid phase compositions) as described herein.
  • the device can be for optical communication, optical computing, or solar energy conversion.
  • the methods can include irradiating the composition at a wavelength corresponding to the sensitizer absorption thereby generating a plurality of photoexcited sensitizers, allowing the plurality of photoexcited sensitizers to simultaneously transfer their energies to a higher-energy state on the conjugated polymer, and detecting luminescence in a spectral region characteristic of the conjugated polymer activated by the photoexcited sensitizers.
  • imaging methods comprising administering to a subject a composition as described herein, irradiating the composition at a wavelength corresponding to the sensitizer absorption, and detecting luminescence in a spectral region characteristic of the conjugated polymer activated by the plurality of photoexcited sensitizers are also provided.
  • Example 1 Polymer-based Cooperative Energy Pooling (CEP)
  • acceptor polymers were purchased from American Dye Source. HIDC was purchased from Exciton and ZnPC was purchased from Alfa Aesar. All materials were used as received.
  • acceptor and polymer chromophores were separately mixed into ⁇ 30 g/L solutions in THF solvent. These solutions were blended together in a ratio of 40 parts acceptor to one part sensitizer. This blend solution was then coated onto a glass substrate using a Zehntner ZAA 2300 blade applicator with the platen at room temperature, a blade height of 75 pm and a blade speed of 99 mm s to produce films -250-300 nm thick with 20-25 nm rms roughness. Glass substrates were cleaned via sonication in acetone and methanol for 5 minutes each and subsequent UV-ozone treatment for 2 minutes before film deposition.
  • Blend films were fabricated via blade coating onto glass substrates and were optimized for maximum film thickness in order to maximize the detectable CEP emission signal.
  • the blade coating was carried out with a blade height of 75 gm above the substrate with the blade moving at 99 mm s with the substrate at room temperature and a stock solution of - 30 g/L. Stylus profilometry measurements determined that the films were approximately 250-300 nm in thickness with 20-25 nm rms roughness.
  • Spectroscopy methods All absorption data was taken on a VWR UV-1600PC Scanning Spectrophotometer. All emission spectra were taken on a LaserStrobe spectrometer from Photon Technology International using a GL-3300 nitrogen laser and GL-302 dye laser attachment, also from Photon Technology International. Upconverted emission spectra were measured with the emission filtered by a 500 nm short-pass filter from Thorlabs, model FES0500, to prevent reflected excitation light from interfering with the measured emission signal. Laser power was measured with a 919P-003-10 thermopile sensor from Newport.
  • Quantum yield measurements were taken in a 4P-GPS-053-SL spectralon integrating sphere from Labsphere with some homebuilt ports and sample holders coated in a diffuse reflective coating mixed according to Knighton c/ a/. (North 4-6 (1981)). All spectra were corrected for the spectral responsivities of the systems used for data collection.
  • Transient absorption measurements were on the system described in Tseng et al. (Eng. Med. Biol. Soc. 2008. 30 th Annu. Int. Conf. IEEE 2004 (2013)).
  • the fundamental excitation pulse was generated using an amplified Ti: sapphire laser from Spectra-Physics (Solstice, 800 nm, 1 kHz, -150 fs pulse FWHM, 3.5 mJ/pulse max) which excited a TOPAS-C optical parametric amplifier from Light Conversion to generate the variable-wavelength (400 or 677 nm) pump pulse used in the experiment.
  • the white light probe light was generated via a portion of the Ti: sapphire beam impinging upon a sapphire plate, the output of which was split into a probe and a reference beam.
  • the pump pulses were passed through a depolarizer and chopped by a synchronized chopper to 500 Hz before reaching the sample.
  • the pump and probe beams were focused to overlap on the sample.
  • the transmitted probe and reference beams were coupled into optical fibers and sent to multichannel spectrometers with CMOS sensors with 1 kHz detection rates where the reference signal was used to correct the probe signal for pulse-to-pulse fluctuations in the white-light continuum.
  • the time delay between the pump and probe pulses was controlled by a motorized delay stage. All experiments were conducted at room temperature.
  • the change in absorbance signal was calculated from the intensities of sequential probe pulses with and without the pump pulse excitation. All data was measured at using randomized time points, meaning that the data was not taken in sequential time steps in order to avoid any artifacts resulting from beam damage to the sample over time. Each spectrum was taken in less than two minutes of time in order to minimize sample burning from beam exposure, and every spectrum was measured at 10 different locations on the film and averaged together afterwards to improve signal -to-noise. ZnPC spectra were taken at 0.1 mJ/pulse excitation intensity while ADS 128 and CEP film spectra were taken with at 25 pj excitation intensity, all with a beam spot of -200 pm diameter. All data was corrected for chirp in the excitation pulse and any variance of TO between measurements.
  • Spectral properties of cooperative energy pooling polymer systems Since the 2PA spectrum of the acceptor determines the emission properties required of the sensitizer, a step in making the present CEP system was to identify strong 2PA acceptors.
  • the fluorene moiety has good 2PA properties, and polymers incorporating fluorene derivatives have impressively large 2PA cross-sections.
  • Four variations of fluorene polymers and co-polymers (displayed in Figure 1 A- Figure ID) were selected as candidates due to their potential for strong 2PA in the wavelength range of interest. These polymers were purchased from American Dye Source and used as received to make solutions in THF solvent. The 2PA cross-section of these molecules was measured using the two-photon excitation fluorescence method.
  • the upconverted wavelength be in the near-IR range.
  • the strong 2PA cross-section and extension into the near-IR made the ADS 128 and ADS259 polymers particularly appealing as acceptors for CEP.
  • Combinatorial testing of these polymers in blend films with various NIR dyes revealed optimized CEP upconversion yields in pairings of ADS 128 with zinc phthalocyanine (ZnPC) and ADS259 with 1,1,3,3,3,3-Hexamethyl-indodicarbocyanine iodide (HIDC).
  • ZnPC zinc phthalocyanine
  • HIDC 1,1,3,3,3,3-Hexamethyl-indodicarbocyanine iodide
  • Blend films were fabricated following the recipe in the methods section.
  • the sensitizeracceptor blend ratio is another key factor in optimizing the CEP emission signal. Films of various sensitizer/acceptor blend ratios were prepared, with a 1 :40 sensitizer/acceptor ratio producing the largest upconverted signal.
  • This blend ratio indicates that both ZnPC and HIDC exhibit strong aggregation-induced self-quenching and require low concentrations in order to maintain excited-state lifetimes long enough for effective CEP to occur. There is mention in the literature of strong aggregation-induced non-radiative decay in ZnPC, further validating this claim.
  • both of these polymer CEP systems exhibit minimal overlap between the acceptor emission spectrum and the sensitizer absorption spectrum, indicating that energy loss due to FRET from acceptor to sensitizer will play a minimal role.
  • Excitation of the pristine acceptor at the same wavelengths as that used for CEP film excitation resulted in minimal upconverted emission, less than one tenth the emission of the corresponding CEP blend films when excited at the same wavelength, indicating that the CEP process is responsible for the vast majority of the observed upconversion.
  • Excitation dependence and quantum yield The excitation dependence of upconverted emission can be a strong indicator of the efficiency of the upconversion process.
  • the turnover point in an excitation dependence graph namely where the excitation dependence transitions from being quadratically dependent on excitation intensity to linearly dependent, is an indicator of what excitation intensities are needed for the upconversion process to run most efficiently.
  • a quadratic dependence on excitation intensity indicates that energy pathways other than upconversion are dominant, and hence that much of the absorbed energy is being lost to other energetic pathways before being upconverted.
  • linear upconversion dependence on excitation intensity indicates both an improved efficiency of upconversion as well as a constant internal quantum yield of upconversion.
  • Transient Absorption Spectroscopy is a powerful tool capable of measuring the unique “fingerprint” of a material by detecting changes in the excited- and ground-state-absorption spectra of the material as a function of time after an excitation pulse.
  • This change in optical density, or AOD is the transient absorption (TA) signal that allows for the identification of distinct excited species within a sample based both on their spectral properties as well as their decay lifetimes as described by Berera et al.
  • TA transient absorption
  • CEP CEP
  • TAS provides an opportunity to directly observe the excitation of the sensitizer chromophore and follow the energy transfer to the acceptor over time after the initial excitation pulse. This type of measurement provides not only direct evidence for CEP energy transfer upconversion but also indicates the time-scales on which CEP operates.
  • transient absorption measurements were taken of pristine films of ZnPC and ADS 128.
  • ADS 128 has uniquely identifiable features centered at 469 nm and 515 nm, with a slight shoulder feature at 555 nm, all of which have -AOD signals.
  • the shape of the spectra changes over time, as noticeable in the absence of the 515 nm and 555 nm features after -100 ps, indicating that each of the features in the transient signal of the acceptor have distinct decay rates.
  • the TA spectrum of ZnPC (Figure 5 A- Figure 5B) has a broad plateau extending from -430-600 nm with a +AOD signal that is composed to sub-features at 485 nm, 530 nm, and 596 nm, each with distinct decay rates and matching similar data in the literature.
  • the feature at 596 nm has a noticeably faster rise and decay time than the other features, further complicating any lifetime analysis.
  • the acceptor and sensitizer chromophores have distinct and uniquely identifiable features
  • the fact that the main features of ADS 128 and ZnPC overlap in wavelength, have opposite AOD signals, and have distinct lifetimes indicates that the signal from the CEP blend film will be a complex superposition of the two signals as a function of time.
  • the TA signal from the CEP blend film does appear to contain components from both sensitizer and acceptor TA spectra.
  • the CEP blend film exhibits a clear plateau extending from 485-590 nm that corresponds to a similar feature in the sensitizer spectrum, as well as a dip centering around 469 nm that corresponds to the acceptor signal peak.
  • Analyzing the TA signal of the CEP blend film is somewhat complex due to the myriad energetic processes occurring within and among each of the chromophore types. As discussed above, the goal of this analysis is to characterize the process of CEP energy transfer from sensitizer to acceptor. Keeping this in mind, analysis of TA signals that are relevant primarily to the internal processes within a chromophore (i.e. the various peaks and associated lifetimes in the sensitizer or acceptor spectra) as well as signals related to processes that occur after the CEP process (i.e. any evolution of the signal components corresponding to the acceptor after its initial excitation) are discussed. What remains is the evolution of the sensitizer signal after excitation and its subsequent energy loss processes (both CEP and various internal decay processes) as well as the growth of the acceptor signal due to CEP energy transfer from the sensitizer.
  • the ability to accurately identify the various features present in the TA data is necessary so that they may be properly assigned to their sources. This is made somewhat easier by the fact that in the range of interest (-440-600 nm) the acceptor signal is entirely -AOD while the sensitizer signal is entirely +AOD.
  • the 469 nm feature's kinetic trace has a delayed rise compared to the others with a subsequent small rise to +AOD values. Since the kinetic trace of the acceptor at 469 nm never exhibits a +AOD signal, this rise was attributed to excitation in the sensitizer. Since the anomalous ultrafast signal in ADS 128 is entirely absent after 200 fs and the ZnPC signal is entirely +AOD, all -AOD signal at 469 nm after -1 ps can be attributed to the main TA feature of the acceptor, and hence to acceptor states excited by the CEP process.
  • this 469 nm feature proceeds to decrease at a much faster rate than the other features and after a few 10s of picoseconds exhibits a -AOD signal.
  • the negative value of this 469 nm feature is significant because it allows positive identification of this feature as corresponding to the excited acceptor.
  • the ZnPC TA signal maintains a relatively uniform +AOD value throughout its entire decay lifetime, which suggests that any deviation from this flat, positive signal is due to excited acceptor. However, deviation from a flat signal would not be conclusive proof of excited acceptor states.
  • a hypothetical +AOD signal at 469 nm that had reduced OD compared to the rest of the plateau signal at longer wavelengths could potentially be caused by a change of shape of the sensitizer signal when in a blend film. Evolution of this hypothetical feature towards reduced, but still positive, OD could potentially indicate either increased acceptor excitation or simple decay of sensitizer excitation without the possibility of distinguishing between the two.
  • the feature at 469 nm is negative and since the sensitizer signal has no -AOD components at any point in time it would be impossible for the TA signal to exhibit -AOD without the presence of excited acceptor chromophores.
  • the -AOD may be either due solely to excited acceptors or due to a superposition of positive signal from excited sensitizers and a stronger negative signal from excited acceptor states, but either interpretation indicates that the acceptor has successfully been excited and hence CEP must have occurred.
  • the remaining pathway forward is a general estimate of the timescale on which CEP occurs. Since the feature at 469 nm begins its negative slope in the 1-10 ps timescale and flattens out by -500 ps, it can be estimated that the timescale of CEP in this system is in the range of tens-to-hundreds of picoseconds.
  • the endurance of the -AOD signal at 469 nm past 1 ns in the blend film is notable and potentially indicates excited acceptor states with lifetimes longer than hundreds of picoseconds. It is possible that the anomalously long lifetime of the CEP-excited state is due to morphological selectivity of the CEP process. For instance, CEP is more likely to occur when there is a minimal separation distance between the sensitizers and the acceptor, and hence CEP energy transfer is likely to preferentially occur to acceptor chromophores whose nearest neighbors are sensitizers rather than other acceptors.
  • sensitizer One aspect of the CEP system in these polymer films was the self-quenching behavior of the sensitizer.
  • the use of sensitizers with high QY even when aggregated would directly increase both the CEP rate but also the CEP radius.
  • the isolation of sensitizer chromophores in these systems also drastically reduces the diffusivity of sensitizer exciton. An overly small diffusivity will result in minimal CEP yields.

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Abstract

L'invention concerne des systèmes de regroupement d'énergie coopératifs basés sur polymères accepteurs . Ces systèmes présentent une excitation retardée de l'accepteur lorsqu'il est excité à des longueurs d'onde d'absorption de sensibilisateur, et le traitement d'événements complexes (CEP) affiché se produisant sur une échelle de temps de dizaines à centaines de picosecondes.
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